EP1445370B1 - Agent d'encollage pour fibre de carbone, procede pour encoller une fibre de carbone au moyen dudit agent, fibre de carbone encollee et tissu maille ou textile tisse au moyen de ladite fibre de carbone - Google Patents

Agent d'encollage pour fibre de carbone, procede pour encoller une fibre de carbone au moyen dudit agent, fibre de carbone encollee et tissu maille ou textile tisse au moyen de ladite fibre de carbone Download PDF

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Publication number
EP1445370B1
EP1445370B1 EP02755686A EP02755686A EP1445370B1 EP 1445370 B1 EP1445370 B1 EP 1445370B1 EP 02755686 A EP02755686 A EP 02755686A EP 02755686 A EP02755686 A EP 02755686A EP 1445370 B1 EP1445370 B1 EP 1445370B1
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EP
European Patent Office
Prior art keywords
carbon fiber
carbon fibers
sizing agent
water
sizing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02755686A
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German (de)
English (en)
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EP1445370A1 (fr
EP1445370A4 (fr
Inventor
Naoki c/o Mitsubishi Rayon Co. Ltd SUGIURA
Norihito c/o Mitsubishi Rayon Co. Ltd MAKI
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Mitsubishi Rayon Co Ltd
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Mitsubishi Rayon Co Ltd
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Publication of EP1445370A4 publication Critical patent/EP1445370A4/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • the present invention relates to a carbon fiber sizing agent, a carbon fiber sizing method using said sizing agent, sized carbon fibers and fabrics using said carbon fibers.
  • Carbon fibers used as reinforcing fibers and so forth of fiber-reinforced composite are fibers in which no less than 90 weight % of the chemical composition is composed of carbon, and which are produced by using regenerated cellulose, polyacrylonitrile (PAN) or pitch and so forth as starting material. These carbon fibers are divided into, for example, high-strength carbon fibers, high-modulus carbon fibers and so forth.
  • carbon fibers are lightweight, have particularly superior properties with respect to specific strength and specific modulus and also have superior heat resistance and chemical resistance, they are particularly effective as reinforcing fibers of fiber-reinforced composite, and are used over a wide range of applications.
  • resin compounds such as epoxy resin or inorganic compounds such as cement and ceramics are used for the matrix of fiber-reinforced composite using carbon fibers as reinforcing fibers, and fiber-reinforced composite are formed that have superior mechanical properties.
  • carbon fibers have also come to be used as reinforcing fibers of short-fiber reinforced composite materials. For example, after chopping carbon fibers into the form of chopped carbon fibers, they are dispersed in water to produce paper containing randomly dispersed chopped carbon fibers and so forth. In addition, chopped carbon fibers are also uniformly mixed and stirred into an inorganic matrix slurry such as concrete to produce a short-fiber reinforced composite in which chopped carbon fibers are randomly dispersed.
  • carbon fibers are typically treated with a water-soluble sizing agent followed by chopping.
  • Preferable sizing agents used for this purpose are provided with superior solubility in water, while also being able to impart both the necessary convergence required for forming stable chopped carbon fibers as well as superior uniform tow dispersibility in water to the carbon fibers.
  • examples of known sizing agents include sizing agents composed of bisphenol type polyalkylene ether epoxy compounds (Japanese Unexamined Patent Application, First Publication No. Sho 61-28074 ), sizing agents composed of compounds in which several ten molecules of alkylene oxide are added to bisphenol A (Japanese Unexamined Patent Application, First Publication No. Hei 1-272867 , Japanese Unexamined Patent Application, First Publication No. 7-9444 ), polyvinyl alcohol and water-soluble thermoplastic resins such as water-soluble Nylon resin (Japanese Examined Patent Application, Second Publication No. Hei 5-4348 or Japanese Patent Publication No. 2838309 ).
  • the sizing agents composed of bisphenol type polyalkylene ether epoxy compounds indicated in Japanese Unexamined Patent Application, First Publication No. Sho 61-28074 have comparatively satisfactory converging performance and allow the obtaining of carbon fibers having superior processability and other workability when formed into chopped carbon fibers or fabrics as a result of providing a glycidyl group in the compound serving as said sizing agent.
  • these sizing agents have the disadvantages of being sticky due to the glycidyl group present in the compound, having inadequate solubility in water, and preventing the obtaining of carbon fibers having satisfactory uniform tow dispersibility in water.
  • sizing agents composed of a compound in which several ten molecules of alkylene oxide are added to bisphenol A indicated in Japanese Unexamined Patent Application, First Publication No. Hei 1-272867 and Japanese Unexamined Patent Application, First Publication No. Hei 7-9444 is able to impart superior uniform tow dispersibility in water to carbon fibers as a result of having superior solubility in water.
  • this type of sizing agent composed of a compound containing ethylene oxide has somewhat weak converging performance that can be imparted to carbon fibers, in order to obtain carbon fibers having adequate convergence required for forming stable chopped carbon fibers and superior processability and other workability when forming into fabrics, it has the disadvantage of requiring a large amount of sizing agent to be adhered to the carbon fibers.
  • the stickiness of this type of sizing agent increases as a result of adsorbing moisture in the air due to the presence of hydrophilic groups such as (-CH 2 -CH 2 -O-) in its molecules thereby resulting in sticking which lowers the processability and other workability of the carbon fibers when formed into fabrics. Consequently, in the case of using this type of sizing agent, the amount of sizing agent adhered must be strictly controlled in order to provide satisfactory processability and other workability to the resulting carbon fiber bundles, thereby increasing the complexity of the production process.
  • sizing agents composed of polyvinyl alcohol or a water-soluble thermoplastic resin such as water-soluble Nylon resin indicated Japanese Examined Patent Application, Second Publication No. Hei 5-4348 or Japanese Patent Publication No. 2838309 have superior solubility in water as well as satisfactory converging performance. Consequently, they are able to impart adequate convergence required for forming into stable chopped carbon fibers as well as superior processability and other workability when forming into fabric to the carbon fibers.
  • carbon fibers imparted with polyvinyl alcohol have superior uniform tow dispersibility in an aqueous solution in the vicinity of pH 7, uniform tow dispersibility in acidic or alkaline aqueous solutions is inadequate.
  • carbon fibers imparted with water-soluble Nylon resin have superior uniform tow dispersibility in acidic aqueous solutions, their uniform tow dispersibility in neutral or alkaline aqueous solutions is inadequate.
  • Document JP 5106164 A discloses carbon fiber and a carbon fiber-reinforced resin composition produced by using the same.
  • the surface of a carbon fiber is coated with a sizing agent consisting of a copolymer having a monomer composition composed of a diamine compound, a dicarboxylic compound and a glyciylated polyalkylene oxide derivative, and an antistatiy agent containing a surfactant.
  • Document JP 09003777 A describes a sizing agent for a carbon fiber which is produced by dissolving a water-soluble polyamide resin composed of polyamide/polyethylene oxide copolymer and a non-ionic or cationic surfactant in distilled water under agitation. Furthermore, acetic acid is added to the sizing agent.
  • Patent JP 2000/054269 A deals with a carbon fiber for a chopped strand and a desized knit or a woven fabric.
  • the carbon fiber is obtained by attaching a sizing composition comprising one or more kinds of surfactants and composed of a polyoxyethylene group and an C 8-18 alkyl group, and a surfactant obtained by binding a propylene oxide group with the surfactant, and one or more kinds of polyvinyl alcohol-based water-soluble thermoplastic resins.
  • a problem to be solved by the present invention is to provide a carbon fiber sizing agent that has satisfactory solubility in water over a wide pH range, and is able to impart to carbon fibers adequate convergence required for forming stable chopped carbon fibers, superior workability (e.g., processability) when forming fabrics, and satisfactory uniform tow dispersibility in water over a wide pH range.
  • Another problem to be solved by the present invention is to provide a carbon fiber sizing method for carrying out effective sizing using the aforementioned sizing agent, sized carbon fibers treated with the aforementioned sizing agent, and a fabric that uses said carbon fibers.
  • a carbon fiber sizing agent of the present invention composed in the manner described below, a carbon fiber sizing method that uses said sizing agent, sized carbon fibers and a fabric that uses said carbon fibers.
  • the carbon fiber sizing agent of the present invention is comprised of water-soluble thermoplastic resin and amphoteric surfactant within a weight ratio range of 6/1 to 1/3.
  • the amphoteric surfactant is a betaine type amphoteric surfactant, and preferably an alkylimidazoline-based betaine type amphoteric surfactant.
  • the water-soluble thermoplastic resin is preferably a water-soluble Nylon resin.
  • the carbon fiber sizing method of the present invention is comprised of treating carbon fibers with a sizing liquid containing the carbon fiber sizing agent of the present invention having the aforementioned constitution.
  • the sized carbon fibers of the present invention are comprised by adhering the carbon fiber sizing agent of the present invention having the aforementioned constitution to their surfaces, and the present invention can be preferably applied to chopped carbon fibers in particular.
  • the fabric of the present invention uses the sized carbon fibers of the present invention having the aforementioned constitution in at least a portion thereof.
  • the carbon fiber sizing agent of the present invention contains a water-soluble thermoplastic resin and a betaine type amphoteric surfactant, and the weight ratio of the water-soluble thermoplastic resin and betaine type amphoteric surfactant is within the range of 6/1 to 1/3. According to this composition, a carbon fiber sizing agent can be provided that has satisfactory solubility in water over a wide pH range, and is able to impart to carbon fibers adequate convergence required for forming into stable chopped carbon fibers, superior workability (e.g., processability) for forming a fabric, and satisfactory uniform tow dispersibility in water over a wide pH range.
  • Amphoteric surfactants used in combination with the aforementioned water-soluble thermoplastic resin include carboxylate type amphoteric surfactants.
  • amphoteric surfactants functions as anionic surfactants in alkaline aqueous solutions and cationic surfactants in acidic aqueous solutions, carbon fiber sizing agents containing such a surfactant have superior solubility in water over a wide pH range.
  • Betaine type amphoteric surfactant such as carboxybetaine type amphoteric surfactant or sulfobetaine type amphoteric surfactant are used since they are able to impart even more superior uniform tow dispersibility to carbon fibers. Moreover, they are also used since there is no decrease in hydrophilic properties at the isoelectric point (where anions and cations are in balance) as is observed with carboxyamino acid type amphoteric surfactants.
  • carboxybetaine type amphoteric surfactants examples include alkyldimethyl betaine type, alkylamide-alkyl betaine type, alkylimidazoline betaine type and hydroxyalkylimidazoline betaine type amphoteric surfactants.
  • alkylimidazoline betaine type amphoteric surfactants makes it possible to impart particularly superior uniform tow dispersibility to carbon fibers.
  • the aforementioned betaine type amphoteric surfactant used in combination with the water-soluble thermoplastic resin may be only one type or a combination of a plurality of types.
  • water-soluble thermoplastic resins that can be used in the carbon fiber sizing agent of the present invention, examples of which include polyvinyl alcohol, water-soluble Nylon resin, water-soluble urethane resin, acrylamide resin, acrylamide-vinyl acetate copolymer resin, polyacrylic ester resin and methyl cellulose.
  • water-soluble Nylon resin is particularly preferable since carbon fibers can be obtained having superior convergence and uniform tow dispersibility in water.
  • the water-soluble thermoplastic resin also fulfills the function of improving uniform tow dispersibility in water.
  • the betaine type amphoteric surfactant fulfills the function of improving uniform tow dispersibility in water over a wide pH range.
  • the weight ratio of water-soluble thermoplastic resin and betaine type amphoteric surfactant is required to be within the range of 6/1 to 1/3, and preferably within the range of 2/1 to 1/2.
  • thermoplastic resin and betaine type amphoteric surfactant may also be added within a range that does not impair the object of the present invention.
  • an antifoaming agent may also be added to the carbon fiber sizing agent of the present invention for the purpose of inhibiting air bubbles formed when dispersing in water.
  • the betaine type amphoteric surfactant is a superior foaming agent and the water-soluble thermoplastic resin is a superior foam stabilizing agent since it is a high molecular weight compound. Consequently, when carbon fibers to which are adhered the carbon fiber sizing agent of the present invention are dispersed in water, the sizing agent dissolves in the water, and these compounds begin to act as foaming agents and foam stabilizing agent. Thus, there are many cases in which it is effective to add an antifoaming agent that dissipates the bubbles formed in advance.
  • antifoaming agents that can be used here, examples of which include silicone antifoaming agents, polyalkylene glycol antifoaming agents, higher alcohol emulsion antifoaming agents, metallic soap antifoaming agents and wax emulsion antifoaming agents.
  • Specific examples include silicone oils, silicone resins, surfactant blends of these resins, polyethylene glycol fatty acid esters, pluronic type nonionic surfactants, polypropylene glycol and its derivatives, and acetylene glycol and its derivatives.
  • the carbon fibers to which the carbon fiber sizing agent of the present invention is applied may be carbon fibers obtained from various starting materials such as pitch, rayon and polyacrylonitrile.
  • they may be a high-strength type (low elastic modulus carbon fibers), medium to high elasticity carbon fibers or ultra-high elasticity carbon fibers.
  • the carbon fiber sizing method of the present invention uses a sizing liquid that contains the aforementioned carbon fiber sizing agent. This method can be carried out by contacting said sizing liquid with carbon fibers by a method such as roller immersion or roller contact followed by drying the carbon fibers.
  • a sizing liquid composed of the aforementioned sizing agent or a sizing liquid in which the aforementioned sizing agent is dispersed or dissolved in a water or an organic solvent such as acetone is used for the sizing liquid.
  • a sizing liquid composed of an aqueous solution is superior both industrially and in terms of safety in comparison with a sizing liquid that uses an organic solvent.
  • the amount of sizing agent that adheres to the surface of the carbon fibers as a result of sizing treatment can be regulated by adjusting the concentration and amount of pressing of the sizing liquid.
  • drying can be carried out using hot air, hot plate, hot rollers or various types of infrared heaters.
  • the sized carbon fibers of the present invention have the aforementioned carbon fiber sizing agent adhered to their surfaces.
  • the amount of sizing agent adhered to the carbon fibers should be an amount that imparts adequate convergence to the carbon fibers, results in satisfactory processability and other workability for forming chopped carbon fibers or fabric, and is able to impart superior uniform tow dispersibility in water. More specifically, the adhered amount is preferably 0.3 to 5.0% by weight, and more preferably 0.5 to 3.0% by weight, with respect to the weight of the carbon fibers.
  • the sized carbon fibers can be used to form chopped carbon fibers by cutting to a length of about 1 to 30 mm using a cutter such as a roving cutter or guillotine cutter.
  • a fabric that uses the sized carbon fibers of the present invention is a fabric that at least uses in a portion therein sized carbon fibers provided with adequate convergence, demonstrate minimal generation of fuzzy due to mechanical friction and so forth, and have superior processability and other workability when formed into a fabric.
  • a fabric of the present invention may be that which only uses the aforementioned sized carbon fibers as threads, or may be a mixed knitted blend or mixed woven blend of said carbon fibers with other fibers.
  • other fibers include inorganic fibers such as glass fibers, TYRANNO fibers and SiC fibers, and organic fibers such as aramid, polyester, PP, nylon, polyimide and vinylon fibers.
  • the water-soluble thermoplastic resins (or their aqueous solutions) and the surfactants (or their aqueous solutions) shown in the following Table 1 were mixed as the weight ratios shown in Table 1 to obtain carbon fiber sizing agents as examples and comparative examples of the present invention. Furthermore, the weight ratios referred to here indicate the weight ratios of the pure components.
  • Each of the resulting sizing agents was used as sizing liquids to treat carbon fibers.
  • each of the resulting sizing agents was filled into an immersion tank provided with free rollers inside.
  • carbon fiber bundles Mitsubishi Rayon Co., Ltd: "PYROFIL TR50SX", number of filaments: 12000, strand strength: 5,000 MPa, strand elastic modulus: 242 GPa
  • the carbon fiber bundles were removed from the tank and dried with hot air to obtain sized carbon fiber bundles which were then wound onto bobbins.
  • Each of the sized carbon fiber bundles were unwound from its bobbin and gently immersed in (a) aqueous nitric acid solution adjusted to pH 2, (b) ion exchange water adjusted to pH 7 and (c) aqueous calcium hydroxide solution adjusted to pH 12.
  • the uniform tow dispersibility of the carbon fiber bundles at this time was evaluated according to the dispersibility index shown below. Furthermore, a dispersibility index of 3 or higher indicates satisfactory uniform tow dispersibility for carbon fibers.
  • Each of the sized carbon fiber bundles were unwound from its bobbin and continuously cut to a length of 6 mm with a roving cutter to form chopped carbon fibers.
  • the workability at this time was evaluated based on the following standards.
  • the sized carbon fiber bundles were woven into a plain weave fabric having a total thread density of 6/inch and a width of 1 m by a rapier-type loom at a weaving speed of 40 cm/minute using each of the carbon fiber bundles as the weft and warp.
  • the ease of fabric production at that time was evaluated based on the following standards.
  • Comparative Examples 2, 5 to 7and 10 which were not blended with a surfactant itself
  • Comparative Examples 3 and 4 which were blended with a surfactant but not an amphoteric surfactant
  • Comparative Examples 8 and 9 which were blended with betaine type amphoteric surfactant, but the weight ratio of water-soluble thermoplastic resin and betaine type amphoteric surfactant was outside the range of 6/1 to 1/3, carbon fiber bundles that satisfied all the requirements of uniform tow dispersibility, workability when formed into chopped carbon fibers and ease of fabric production were unable to be obtained despite having undergone sizing treatment.
  • the carbon fiber sizing agent of the present invention has satisfactory solubility in water over a wide pH range, and simultaneous to imparting to the carbon fibers adequate convergence required for forming into stable chopped carbon fibers and superior workability (e.g., processability) when forming into a fabric, it is also able to impart superior uniform tow dispersibility in water over a wide pH range.
  • the carbon fiber sizing method of the present invention is carried out by using a sizing liquid that contains the aforementioned carbon fiber sizing agent of the present invention, and simultaneous to imparting to the carbon fibers adequate convergence required for forming into stable chopped carbon fibers and superior workability (e.g., processability) when forming into a fabric, it is also able to impart superior uniform tow dispersibility in water over a wide pH range.
  • the sized carbon fibers of the present invention are those in which the aforementioned sizing agent of the present invention is adhered to their surfaces, and are provided with adequate convergence required when forming into stable chopped carbon fibers and superior workability (e.g., processability) when forming into a fabric, while also being provided with superior uniform tow dispersibility in water over a wide pH range.
  • a fabric that uses the sized carbon fibers of the present invention demonstrates affinity to water over a wide pH range, it is suitable for applications such as immersing said fabric in an aqueous matrix in order to impregnate the fabric with that matrix.
  • the present invention can be carried out in various other forms without deviating from its major characteristics.
  • the aforementioned modes for carrying out the present invention merely indicate examples thereof, and should not be understood to limit the invention in any way.
  • the scope of the present invention indicates the scope of claim for patent, and is not constrained in any manner by the text of the description.
  • all variations and modifications falling within the equivalent scope of claim for patent are included within the scope of claim for patent.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (7)

  1. Agent d'encollage pour fibres de carbone comprenant:
    une résine thermoplastique hydrosoluble et un agent tensioactif amphotère de type bétaïne dans une plage de rapport pondéral de 6/1 à 1/3.
  2. Agent d'encollage pour fibres de carbone selon la revendication 1; dans lequel l'agent tensioactif amphotère de type bétaïne est un agent tensioactif amphotère de type bétaïne à base d'alkylimidazoline.
  3. Agent d'encollage pour fibres de carbone selon la revendication 1/ dans lequel la résine thermoplastique hydrosoluble est une résine de nylon hydrosoluble.
  4. Procédé d'encollage de fibres de carbone comprenant le traitement des fibres de carbone avec un liquide contenant un agent d'encollage de fibres de carbone selon la revendication 1.
  5. Fibres de carbone encollées comprenant un agent d'encollage pour fibres de carbone selon la revendication 1 appliqué par adhérence sur les surfaces des fibres de carbone.
  6. Fibres de carbone encollées selon la J revendication 5, dans lesquelles les fibres de carbone sont des fibres de carbone coupées.
  7. Tissu comprenant les fibres de carbone encollées selon la revendication 5.
EP02755686A 2001-07-31 2002-07-30 Agent d'encollage pour fibre de carbone, procede pour encoller une fibre de carbone au moyen dudit agent, fibre de carbone encollee et tissu maille ou textile tisse au moyen de ladite fibre de carbone Expired - Lifetime EP1445370B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2001232410 2001-07-31
JP2001232410 2001-07-31
PCT/JP2002/007728 WO2003012188A1 (fr) 2001-07-31 2002-07-30 Agent d'encollage pour fibre de carbone, procede pour encoller une fibre de carbone au moyen dudit agent, fibre de carbone encollee et tissu maille ou textile tisse au moyen de ladite fibre de carbone

Publications (3)

Publication Number Publication Date
EP1445370A1 EP1445370A1 (fr) 2004-08-11
EP1445370A4 EP1445370A4 (fr) 2006-05-24
EP1445370B1 true EP1445370B1 (fr) 2008-06-18

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Application Number Title Priority Date Filing Date
EP02755686A Expired - Lifetime EP1445370B1 (fr) 2001-07-31 2002-07-30 Agent d'encollage pour fibre de carbone, procede pour encoller une fibre de carbone au moyen dudit agent, fibre de carbone encollee et tissu maille ou textile tisse au moyen de ladite fibre de carbone

Country Status (8)

Country Link
US (1) US7135516B2 (fr)
EP (1) EP1445370B1 (fr)
JP (1) JP4094546B2 (fr)
CN (1) CN1261637C (fr)
AT (1) ATE398700T1 (fr)
DE (1) DE60227188D1 (fr)
ES (1) ES2306775T3 (fr)
WO (1) WO2003012188A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014180779A1 (fr) 2013-05-08 2014-11-13 Ems-Patent Ag Matériaux de remplissage doté d'un revêtement de surface en polyamides hydrosolubles

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US7135516B2 (en) 2006-11-14
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US20040197555A1 (en) 2004-10-07
JPWO2003012188A1 (ja) 2004-11-18
EP1445370A1 (fr) 2004-08-11
JP4094546B2 (ja) 2008-06-04
WO2003012188A1 (fr) 2003-02-13
CN1537188A (zh) 2004-10-13
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ATE398700T1 (de) 2008-07-15
EP1445370A4 (fr) 2006-05-24

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